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Double heterojunction nanorods enable both electroluminescence and light harvesting capabilities within the same device structure, providing a promising platform for energy-scavenging displays and related applications. However, the efficiency of the photovoltaic mode remains modest for useful power conversion and may be challenging to improve without sacrificing performance in electroluminescence. Through a facile on-film partial ligand exchange with benzenethiol integrated into the device fabrication step, we achieve an average of more than threefold increase in power conversion efficiency while maintaining the maximum external quantum efficiency and the maximum luminance in the LED mode. The improved photovoltaic performance is mainly due to the increase in the short circuit current, which we attribute to the enhanced charge separation afforded by the partial ligand exchange. The recovery of the photoluminescence lifetime under the forward bias suggests that the hole traps introduced by benzenethiols are filled prior to reaching the voltage at which light emission begins, allowing LED performance to be maintained and possibly improved. [ABSTRACT FROM AUTHOR]

In recent years, nanozymes have attracted particular interest and attention as catalysts because of their high catalytic efficiency and stability compared with natural enzymes, whereas how to use simple methods to further improve the catalytic activity of nanozymes is still challenging. In this work, we report a trimetallic metal–organic framework (MOF) based on Fe, Co and Ni, which was prepared by replacing partial original Fe nodes of the Fe-MOF with Co and Ni nodes. The obtained FeCoNi-MOF shows both oxidase-like activity and peroxidase-like activity. FeCoNi-MOF can not only oxidize the chromogenic substrate 3,3,5,5-tetramethylbenzidine (TMB) to its blue oxidation product oxTMB directly, but also catalyze the activation of H2O2 to oxidize the TMB. Compared with corresponding monometallic/bimetallic MOFs, the FeCoNi-MOF with equimolar metals hereby prepared exhibited higher peroxidase-like activity, faster colorimetric reaction speed (1.26–2.57 folds), shorter reaction time (20 min) and stronger affinity with TMB (2.50–5.89 folds) and H2O2 (1.73–3.94 folds), owing to the splendid synergistic electron transfer effect between Fe, Co and Ni. Considering its outstanding advantages, a promising FeCoNi-MOF-based sensing platform has been designated for the colorimetric detection of the biomarker H2O2 and environmental pollutant TP, and lower limits of detection (LODs) (1.75 μM for H2O2 and 0.045 μM for TP) and wider linear ranges (6–800 μM for H2O2 and 0.5–80 μM for TP) were obtained. In addition, the newly constructed colorimetric platform for TP has been applied successfully for the determination of TP in real water samples with average recoveries ranging from 94.6% to 112.1%. Finally, the colorimetric sensing platform based on FeCoNi-MOF is converted to a cost-effective paper strip sensor, which renders the detection of TP more rapid and convenient. [ABSTRACT FROM AUTHOR]

The development of concise and efficient methods to construct bithiophene derivatives is an appealing task in the fields of organic chemistry and organic functional materials. Herein, we summarize our recent efforts towards the development of catalytic oxidative C–H cyclization reactions of thiophenol derivatives with 1,3-diynes, which provides a straightforward and effective synthetic approach to both symmetrical and nonsymmetrical 3,3′-bibenzothiophenes. This work is expected to stimulate the application of catalytic oxidative C–H annulation of aromatics with 1,3-diynes for the exploitation of organic functional materials. [ABSTRACT FROM AUTHOR]

Crude oil and petroleum products contain various types of sulfur compounds: aliphatic and aromatic mercaptans, hydrogen sulfide, sulfides, disulfides, thiophene derivatives, etc. Some of these may dissolve in water only slightly, but their toxicity and corrosiveness indicate that even these small amounts should be eliminated from water. This work examines, for the first time, the removal of thiophenol (synonyms: benzenethiol, phenyl mercaptan) from water using sepiolite. This clay mineral (evaluated by SEM analysis) is an attractive natural sorbent characterized by its microporosity, which results from its crystalline structure and large specific surface area. Because the structure of thiophenol changes depending on the pH of the aqueous solution (due to the loss of a proton), the research was conducted at pH 4, 7 and 9. The detection of thiophenol in aqueous solution was investigated using UV spectroscopy. It was found that the adsorption of thiophenol is possible, but it occurs only in an acidic environment (pH 4). No sorption is observed at pH 7 or 9. The adsorption of thiophenol at pH 4 does not change significantly after changing the ionic strength of the aqueous solution (distilled water, 0.01 NaCl and 0.1 NaCl). The adsorption capacity of sepioliteis approximately 0.23–0.34 mg/g. Studies using infrared spectroscopy and fitting of Freundlich and Langmuir isotherm models to the results of adsorption experiments indicate that adsorption on unmodified sepiolite follows a physisorption mechanism. Additionally, to understand the behavior of thiophenol in the presence of sepiolite across different pH ranges, DFT/PCM/B3LYP/Aug-CC-pVDZ calculations were used to analyze the charge distribution on particular atoms in its structure. [ABSTRACT FROM AUTHOR]

Herein, the synthesis of 2-amino-3,5-dicyano-6-sulfanyl pyridine derivatives has been studied due to wide applications of highly substituted pyridines. At first, Hydrotalcite (HT) with various loading amounts of lanthanum (HT-La) was synthesized. Then, their catalytic activities were investigated for the condensation reaction of benzaldehyde, malononitrile, and thiophenol under reflux condition as a model reaction. The prepared HT nanocatalyst with 10 mol% of La showed the best performance in this multicomponent reaction. In addition, the reusability of the nanocatalyst was studied and the results showed, that the prepared nanocatalyst could be reused several times with an only moderate decrease in activity. Subsequently, HT-La (10 mol%) efficiently catalyzed the one-pot condensation reaction for the synthesis of highly substituted pyridines under reflux conditions. The products were produced with excellent yields, short reaction times, and easy recyclability of the nanocatalyst. [ABSTRACT FROM AUTHOR]

We present herein Brønsted acid‐catalyzed Friedel‐Crafts alkylation of phenols with Donor–Acceptor cyclopropane ketones. The presence of the 1,4‐diphenyl butan‐1‐one and 1,3‐diphenyl propane‐1‐one motifs in various naturally occurring biologically significant molecules inspired us to pursue the direct synthesis of these structural frameworks. Utilizing methanesulfonic acid (MeSO3H) as a catalyst, we achieved a more environmentally friendly and high‐yielding synthesis, owing to its cost‐effectiveness, biodegradability, transition–metal and additives free conditions. Furthermore, we have successfully extended our developed methodology to thiophenols, resulting in the production of sulfur–based butan‐1‐one derivatives in good yields. [ABSTRACT FROM AUTHOR]

Polyether amines are versatile compounds characterized by a flexible structure, consisting of polyoxypropylene and polyoxyethylene as the backbone, with amine groups at each end. They have widespread applications in various industrial processes and daily life. Despite their versatility, the utilization of polyether amines as base catalysts is rare. In this study, one kind of three-arm polyether amine 1 was employed as an environmentally friendly, cost-effective catalyst for the aerobic oxidation of thiophenols, leading to the synthesis of disulfides. The oxidative coupling of thiols serves as a fundamental pathway for the production of disulfides, which are vital in both chemical and biological processes. In contrast to known methods for thiol oxidation, this polyether amine-based catalytic process eliminates the need for expensive stoichiometric oxidants and minimizes the formation of over-oxidized by-products. Using a mere 0.5 mol % of the polyether amine 1 as the catalyst, a remarkable > 96% yield was achieved for all 16 tested substrates, encompassing a diverse range of functional groups, under the catalytic aerobic oxidation conditions. Furthermore, it is noteworthy that over 90% of the polyether amine catalyst can be efficiently recovered for reuse without loss of activity, making this a sustainable and cost-effective catalytic approach. [ABSTRACT FROM AUTHOR]

The generation of a low HOMO-LUMO energy gap makes organic polymer-based composites an important class of materials with outstanding catalytic efficiency. The present work describes the simple and direct synthesis of an excellent photocatalyst, PC (C26H16NO7S)n via doping of erythrosine-B dye on sulfone infused poly(2-amino thiophenol) assembly (PA, (C6H4NO2S)n). The O 1 s spectrum displays peaks at 531.8 eV and 533.3 eV, representing the O=C and O–C groups of the in-situ generated fluorescein loaded on PA surface. Through absorption study (Tauc's plot), the optical band gap (Eg) for polymer PA (2.9 eV) and photocatalyst PC (2.1 eV) has been calculated. Further, due to the efficient absorbance in the range of 400–600 nm with a low optical band gap, the applicability of the catalyst, PC has been checked in photocatalytic C–H activation in thiophene, and the generation of C–C bond with p-nitro aryldiazonium salt. [ABSTRACT FROM AUTHOR]

A series of tetraaza‐expanded calix[4]arene analogues (2–4), in which two of the four aryl groups are ethylene‐protected thiophenol components were prepared from tetraaldehyde 1. Two of these strapped macrocycles were characterized crystallographically, as well as the dipalladium complex of 4. The same tetraaldehyde had been previously used for the synthesis of a macrotricycle (5) and a macropentacycle (6), the coordination properties of which have been investigated. In particular, ligand 6 was shown to be able to encapsulate a Cu+ or a Ag+ ion in the tetrahedral coordination pocket offered by a bridgehead nitrogen atom and the three proximal thioether sulfur atoms. [ABSTRACT FROM AUTHOR]

Herein, we have accomplished a simple visible light mediated protocol for the cross dehydrogenative coupling of arylthiols with indoles in excellent yields. Eosin Y disodium salt is used as a photocatalyst for generating the arylsulfur radical under blue light irradiation as confirmed by the quenching, radical scavenging and EPR studies. Among the synthesized arylthioindoles, 5‐bromo‐3‐((4‐methoxyphenyl)thio)‐1H‐indole possess antibacterial properties. These 3‐arylthioindoles were further transformed into indolyl‐3‐arylsulfones and indolyl‐3‐arylsulfoxides, a potent class of non‐nucleoside reverse transcriptase inhibitors against human immunodeficiency virus (HIV) type I. [ABSTRACT FROM AUTHOR]

Efficient approaches to perfluoroalkyl/alkenyl aryl sulfides were accomplished by a C−S coupling reaction under mild conditions. Hexafluoropropylene dimer was employed as a versatile building block for the perfluoroalkylation and perfluoroalkenylation of thiophenol. The application of the synthetic strategy was demonstrated by the high‐yield transformation of a broad range of aryl derivatives. A plausible mechanistic explanation was proposed to elaborate the differences between the two reaction pathways. The methodology provides straightforward and convenient access to aryl sulfides constituting C6 perfluoroalkyl and perfluoroalkenyl substituents. [ABSTRACT FROM AUTHOR]

We have described one-pot multicomponent synthesis of 2-amino-3,5-dicyano-6-phenylthiopyridine incorporated1,2,3-triazole derivatives from triazolyl aldehydes, malononitrile and thiophenol in excellent yields. The antitubercular, antifungal and antioxidant activity for all the synthesized derivatives were evaluated. The antifungal activity results show that the compounds 12a, 12b and 12g were observed more potent than Miconazole with MIC value <25 µg/mL. Whereas, the antitubercular screening against MTB H37Rv strain did not produce any promising results. Furthermore, in silico ADME properties for all the compounds were also studied and exhibited the potential to be developed as an oral drug candidate. [ABSTRACT FROM AUTHOR]

A photochemical rearrangement of O‐aryl thiocarbamates to the corresponding S‐aryl compounds that is triggered by heterogeneous electron transfer between the substrate and photo‐excited titanium dioxide is presented. The rearrangement is the key‐reaction in the three‐step conversion of phenols into the corresponding thiophenols. The described procedure can be performed at room temperature under aerobic conditions using violet LEDs. The rearrangement has been achieved for 24 electron‐rich substrates with yields up to 99 %. A plausible mechanism is proposed based on the substrate scope, spectroscopic studies, and control experiments. [ABSTRACT FROM AUTHOR]

A series of sulfenimide derivatives (1a-i) were investigated as inhibitors of human (hCA-I, hCA-II) and bovine (bCA) carbonic anhydrase enzymes. The compounds were synthesised by the reaction of substituted thiophenols with phthalimide by means of an effective, simple and eco-friendly method and the structures were confirmed by IR, 1H NMR, 13C NMR, MS and elemental analysis. All derivatives except for the methyl derivative (1b) exhibited effective inhibitory action at low micromolar concentrations on human isoforms, but only four derivatives (1e, 1f, 1h, 1i) inhibited the bovine enzyme. The bromo derivative (1f) was found to be strongest inhibitor of all three enzymes with KI values of 0.023, 0.044 and 20.57 µM for hCA-I, hCA-II and bCA, respectively. Results of our study will make valuable contributions to carbonic anhydrase inhibition studies for further investigations since inhibitors of this enzyme are important molecules for medicinal chemistry. [ABSTRACT FROM AUTHOR]

A metal‐free tunable 1,2‐difunctionalization of the terminal alkynes showcasing a tandem installation of C−C and C−S bonds has been developed. The key enabling factor for the approach is the use of acetic acid as an acyl source to synthesize β‐substituted α,β‐unsaturated ketones. The reaction at room temperature leads to the regioselective acylation at the terminal carbon of alkynes, whereas at −78 °C, the acylation occurs at the more substituted carbon. [ABSTRACT FROM AUTHOR]

Organic chemistry has seen a surge in visible‐light‐driven transformations, which offer unique reaction pathways and access to new synthetic possibilities. We aim to provide a comprehensive understanding of state‐of‐the‐art photo‐mediated alkyne functionalization, with a focus on the reactive behavior of vinyl radicals. This review outlines our contributions to the field, including developing new methods for forming carbon‐carbon and carbon‐heteroatom bonds. [ABSTRACT FROM AUTHOR]

An efficient and eco‐friendly method has been developed for the preparation of functionalized 3‐(S)‐arylthioindoles in good to excellent yields from indoles and aryl thiols in water. The coupling reaction was prompted by K2S2O8 in the presence of glucose at room temperature. Broad substrate scope, functional group tolerance, room temperature reactions and metal‐free conditions are the salient features of the developed methodology. [ABSTRACT FROM AUTHOR]

In this study, the sensing mechanism of (2E,4E)-5-(4-(dimethylamino)phenyl)-1-(2-(2,4dinitrophenoxy)phenyl)penta-2,4-dien-1-one (DAPH-DNP) towards thiophenols was investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT). The DNP group plays an important role in charge transfer excitation. Due to the typical donor-excited photo-induced electron transfer (d-PET) process, DAPH-DNP has fluorescence quenching behavior. After the thiolysis reaction between DAPH-DNP and thiophenol, the hydroxyl group is released, and DAPH is generated with the reaction showing strong fluorescence. The fluorescence enhancement of DAPH is not caused by an excited-state intramolecular proton transfer (ESIPT) process. The potential energy curves (PECs) show that DAPH-keto is less stable than DAPH-enol. The frontier molecular orbitals (FMOs) of DAPH show that the excitation process is accompanied by intramolecular charger transfer (ICT), and the corresponding character of DAPH was further confirmed by hole-electron and interfragment charge transfer (IFCT) analysis methods. Above all, the sensing mechanism of the turn-on type probe DAPH-DNP towards thiophenol is based on the PET mechanism. [ABSTRACT FROM AUTHOR]

In this study, O-amino benzenethiol (OABT) was oxidized in one pot using Fe(NO3)3 to produce a novel Fe2S3-Fe2O3/poly O-amino benzenethiol (POABT), which showed a highly uniform morphology. At the same time, from SEM analysis, highly wrinkled porous polypyrrole (Ppy) and porous ball-like POABT structures prepared from the K2S2O8 route were evidenced by SEM and TEM analyses. A nanocomposite pseudo-supercapacitor (SC) was fabricated using Fe2S3-Fe2O3/POABT, and its performance was tested with and without incorporating Ppy in the paste. The results indicate that Ppy significantly increased the specific capacitance (CS) values, indicating an enhancement in charge storage. At a current density of 0.2 A/g, the CS values were 44 F/g and 161 F/g for the paste without and with Ppy, respectively. Additionally, the E was calculated, and the incorporation of Ppy resulted in a significant increase in E, reaching 30 W.h.kg−1; this was significantly higher than the value of 8.18 W.h.kg−1 observed without Ppy materials. This effect is likely due to the improved charge transfer facilitated by the presence of Ppy, as evidenced by the Nyquist plot, where the Rct values were 1.1 Ω and 2.1 Ω with and without Ppy, respectively. Overall, the low cost and significant technical advantages of this capacitor make it a promising candidate for commercial applications. [ABSTRACT FROM AUTHOR]

We used tip-enhanced Raman spectroscopy (TERS) to examine plasmon-driven dimerization of 4-bromothiophenol (4-BTP) into thiophenol (TP) and 4,4′-biphenyldithiol (4,4′-BPDT) on Au and Ni@AuNPs. TERS revealed that cross-coupling of these molecular reactants into 4,4′-BPDT occurred primarily on Ni nano islands rather than the surrounding Au on the surface of Ni@AuNPs. [ABSTRACT FROM AUTHOR]

Photocatalytic processes triggered by graphene‐based photocatalysts under solar light have sparked interest as a new sort of instrument for solar chemical synthesis. Herein we investigated self‐assembled graphene quantum dots (GQDs)/NiSe‐NiO composite photocatalyst for organic transformation as well as dye degradation. The synthesized GQDs/NiSe‐NiO composite photocatalyst has an excellent suitable band gap, high molar extinction coefficient, low toxicity and chemical/thermal stability. The GQDs/NiSe‐NiO composite photocatalyst emerges as a new standard for sulfur oxidation and dye degradation reactions under homemade LED light with high yield. [ABSTRACT FROM AUTHOR]

Under mild irradiation conditions using violet light-emitting diodes, a catalytic amount of a thiolate of N -(4-mercaptophenyl)pivalamide promotes monoselective defluoroalkylation of trifluoroacetates with a variety of aliphatic alkenes in the presence of a formate salt. The reactions allow facile and low-cost synthesis of valuable α,α-difluoro substituted aliphatic carboxylate esters under mild conditions, and demonstrate the dual-functional role of arenethiolates in photocatalysis as both a strong photoreductant in a redox cycle and a hydrogen-atom-transfer catalyst. [ABSTRACT FROM AUTHOR]

A xanthene fluorophore-based probe, Xanth-NO2, has been reported for the detection of thiophenol. Xanth-NO2 exhibited quenched fluorescence in an aqueous buffer due to its aggregate state, which allows a fluorescence turn-on response via the PhSH-induced transetherification process. In an aqueous buffer, the half-time for the reaction of Xanth-NO2 with thiophenol is 15 min. There is a linear overlap between the Xanth-NO2 fluorescence and thiophenol concentrations (0–10 μM), with a 130 nM detection limit. Xanth-NO2 reacted differently with hydrogen sulfide and thiophenol, allowing us to distinguish between these two analytes. Additionally, the ability of Xanth-NO2 to detect thiophenol in the presence of competing molecules or ions was demonstrated. Real-water samples and paper strip-based vapour phase detection of thiophenol were used to show the potential use of the reported probe. [ABSTRACT FROM AUTHOR]

Herein, we investigate the chemical sensing by surface-enhanced Raman scattering regarding two templates of gold nanocolumns (vertical and tilted) manufactured by glancing angle deposition with magnetron sputtering. We selected this fabrication technique due to its advantages in terms of low-cost production and ease of implementation. These gold nanocolumnar structures allow producing a high density of strongly confined electric field spots within the nanogaps between the neighboring nanocolumns. Thiophenol molecules were used as model analytes since they have the principal property to adsorb well on gold surfaces. Regarding chemical sensing, the vertical (tilted) nanocolumnar templates showed a detection threshold limit of 10 nM (20 nM), an enhancement factor of 9.8 × 10 8 (4.8 × 10 8 ), and a high quality of adsorption with an adsorption constant K a d s of 2.0 × 10 6 M − 1 (1.8 × 10 6 M − 1 ) for thiophenol molecules. [ABSTRACT FROM AUTHOR]

This work demonstrates the enhancement in plasmonic sensing efficacy resulting from spatially-localized functionalization on nanostructured surfaces, whereby probe molecules are concentrated in areas of high field concentration. Comparison between SERS measurements on nanostructured surfaces (arrays of nanodisks 110 and 220 nm in diameter) with homogeneous and spatially-localized functionalization with thiophenol demonstrates that the Raman signal originates mainly from areas with high field concentration. TERS measurements with 10 nm spatial resolution confirm the field distribution profiles predicted by the numerical modeling. Though this enhancement in plasmonic sensing efficacy is demonstrated with SERS, results apply equally well to any type of optical/plasmonic sensing on functionalized surfaces with nanostructuring. [ABSTRACT FROM AUTHOR]

A photoredox mediated approach enabling the synthesis of (E)‐β‐iodovinyl sulfones at room temperature using simple alkynes and thiols as the coupling partners in the presence of TBAI as iodine source is reported. The direct conversion of thiols into sulfones following the tandem introduction of C−I and C−S bonds is achieved using SeO2 as an oxidizing agent. The method is viable with a wide range of alkynes and thiols at room temperature, employs mild conditions, and has good yields. Besides, we could also use β‐iodovinyl sulfones as the starting material to access different β‐functionalized sulfone derivatives. [ABSTRACT FROM AUTHOR]

Among sulfur-containing species, thiophenol (PhSH) is highly toxic but is uncommonly studied. Here a novel probe is reported for thiophenol with rapid response and high selectivity. Thiophenol was easily distinguished by this probe from other sulfur-containing species including anions and biothiols. The probe was employed for the determination of thiophenol in several buffer systems and in living cells, demonstrating suitability for future work. [ABSTRACT FROM AUTHOR]

We hereby disclose, a visible light mediated addition of sulfenyl radicals to trialkyl phosphites to access functionalized phosphorothioates. The use of cheap and readily available Eosin Y as a photocatalyst under mild energy efficient conditions bypassing the use of external oxidants forms the chief highlight of the work. The protocol is scalable and mechanistic studies indicate that the reaction proceeds through an ionic‐Arbuzov like pathway from phosphoranyl radicals. [ABSTRACT FROM AUTHOR]

A photoredox approach enabling one-step synthesis of oxazetidines with a free –NH group via the combined use of alkyne, thiophenol, and azide has been reported. The synthesized oxazetidine with the free –NH group was stable enough for various late-stage transformations such as methylation, acetylation, tosylation, and ring-opening reaction to afford synthetically useful α-aminoketones. [ABSTRACT FROM AUTHOR]

The synthetic versatility of thiophenols is offset by their air-sensitivity and foul odor. It is demonstrated that S -aryl isothiouronium salts can be used as precursors to thiyl radicals, extending the practical benefits of these air-stable, odorless salts from ionic to single electron manifolds. The isothiouronium salts are accessed via Ni-catalyzed cross-coupling of (hetero)aryl iodides and thiourea and are isolated as free-flowing solids following anion exchange. Judicious choice of a redox-innocent counteranion enables use of these convenient thiophenol surrogates in radical processes, as is exemplified by the synthesis of non-symmetrical diaryl thioethers via light-promoted S -arylation. [ABSTRACT FROM AUTHOR]

In this work, we present a study on the sensing of chemical molecules with Au nanoparticles coated ZnO film by employing the photo-induced enhanced Raman scattering (PIERS) coupled to the surface-enhanced Raman scattering (SERS). Moreover, the interest of coupling the PIERS to classical SERS (electromagnetic contribution) is to achieve a high sensitivity of detection. In our work, we employed the thiophenol molecule for its quality of adsorption on metals and its small size. For this thiophenol detection, we found a limit concentration of 100 pM, an adsorption capacity ( K A d s ) of 3.2 × 10 6 M − 1 and an analytical enhancement factor of 1.9 × 10 10 . [ABSTRACT FROM AUTHOR]

Palladium-catalyzed C–H thiolation of aryl 2-pyridyl sulfoxide with diaryl disulfides has been achieved. The reaction proceeds selectively at the ortho-position of masked thiophenol. The directing group 2-pyridyl sulfoxide can be further converted to various sulfur functionalities through conventional reduction/oxidation processes. Kinetic isotopic studies and radical quenching experiments were performed to understand the reaction mechanism. [ABSTRACT FROM AUTHOR]

A synthetic method of o‐sulfanylanilines from cyclohexanones, amines, and thiophenols under transition‐metal‐free conditions is disclosed. This is the first report on the direct thioamination of cyclohexanones via N‐iodosuccinimide (NIS) promoted oxidative dehydroaromatization. Non‐aromatic cyclohexanones were smoothly dehydrogenated, and acted as an aryl source using oxygen as a green oxidant. The capacity of the resultant o‐sulfanylanilines for synthesis of N‐arylphenothiazines has been further demonstrated. [ABSTRACT FROM AUTHOR]

The novel and precise design of both a microscopic ligand and macroscopic structure has been demonstrated to improve the stability and potential optical applications of Ag44 clusters. The ligand with designed silane substituents on its thiophenol enabled the synthesized [Ag44(SPhSi(OEt)3)30](PPh4)4 clusters to maintain UV-vis absorption for 13 h when heated at 60 °C in air and be readily coated with silica shells via a one-pot reverse microemulsion method. This composite structure overcomes the issue that non-luminescent Ag44 clusters cannot be applied in photothermal and photoacoustic imaging due to their instability. [ABSTRACT FROM AUTHOR]

Elimination of interfacial thermal resistance is a critical issue to improve the thermal conductivity of graphene-based metal matrix composites. Here, thiophenol groups were employed to construct an interfacial molecular junction between graphene and copper to improve the thermal conduction performance of the graphene/copper composite. The highly delocalized aryl properties of thiophenol groups can facilitate electron tunneling at the interface, thereby increasing the electron thermal conduction and reducing the interfacial thermal resistance between graphene and copper nanoparticles. The resulting thiophenol group linked graphene and copper composite shows a high thermal conductivity of 500.6 W m−1 K−1, which is 1.43 and 1.30 times higher than those of copper (Cu) and pristine graphene–copper composites (Gr–Cu), respectively, and also higher than most reported values via a single phonon thermal conduction route. Placed on a heat source heated from 26 °C to 213 °C within 5 min, the top surface temperature of TP–Gr–Cu increases to 184.2 °C rapidly, whereas those of Gr–Cu and Cu only increase slowly to 61.4 °C and 51.6 °C. This work demonstrates that an interfacial electron thermal conduction route can be built through electron tunneling by constructing a molecular junction between graphene and copper, which can significantly reduce the interfacial thermal resistance and improve the interfacial thermal conductivity. [ABSTRACT FROM AUTHOR]

The detection mechanism of fluorescent probe FQ-DNP (DNP: 2,4-dinitropheno) for PhSH and the detailed ESIPT process of its product 2-(6-(diethylamino) quinolin-2-yl)-3–Hydroxy-4H-chromen-4-one (FQ-OH) have been revealed by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). For FQ-OH, the decreased bond length of H6–N7 and RDG analysis illustrate that the strength of hydrogen bond H6–N7 has been enlarged after photoexcitation, creating a good condition for ESIPT. To illustrate the ESIPT process in detail, the potential energy curves are performed and the transition state reaction energy is calculated. In the S0 state, the FQ-OH could happen proton transfer (PT) to form keto, but the keto form is more unstable than enol form. After photoexcitation, in the S1 state, FQ-OH could happen PT to produce stable keto form. Excited dynamic simulation shows that PT happens at 71.5 fs. The calculated absorption and emission spectra are in agreement with the experimental data, and the calculated Stokes shift is 160 nm. Frontier molecular orbitals (FMOs) and hole–electron analysis show that twisted intramolecular charge transfer (TICT) is responsible for the fluorescent quenching of FQ-DNP. [ABSTRACT FROM AUTHOR]

This short note describes the synthesis of compound 6,6′-di-(2″-thiophenol)-2,2′-bipyridine from its methyl phenyl sulfane precursor via deprotection of the methyl groups. The product as well as the intermediate in the synthetic route have been characterized by UV-Vis spectroscopy, 1H- and 13C-NMR spectroscopy, FT-IR spectroscopy, and HR-MS analysis. This work presents a rare example of tetradentate chelators that bears pyridyl backbones and thiophenol donors for the coordination with 3d-transition metal cations. [ABSTRACT FROM AUTHOR]

Three thiophenol derivatives with different substituent groups, 2-Naphthalenethiol (2-NT), 4-Chlorothiophenol (4-Cl) and p-Toluenethiol (4-MT) were selected to study the corrosion inhibition performance for copper in saline medium. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements, and weight loss tests were performed to compare the effect of different concentrations and various types of thiophenol derivatives on corrosion inhibition performances. Scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and Surface-enhanced Raman spectroscopy (SERS) were utilized to characterize surface morphology and molecular structures of copper samples after corrosion in saline medium or electrochemical tests. Quantum chemical calculations were applied to further investigate the microscopic mechanism of the interaction between thiophenol derivative inhibitor molecules and copper surface. XPS, SERS, and theoretical calculations results indicate that thiophenol derivative inhibitors were adsorbed on Cu surface by Cu–S chemical bond. It was also found that these thiophenol derivative inhibitors could effectively inhibit the corrosion of copper by chemisorption and the efficiency follows the order of 2-NT >4-Cl >4-MT. The larger conjugated aromatic structure in 2-NT may be responsible for the measured higher inhibition efficiency of 2-NT. [ABSTRACT FROM AUTHOR]

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon‐mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark‐field optical microscopy, the plasmon‐mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot‐hole‐driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon‐mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts. [ABSTRACT FROM AUTHOR]

p-Xylylene bis(triphenylphosphonium tribromide) (XBTPPTB ) could be used for selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides as an effective and green reagent, under nonaqueous and aprotic conditions without catalyst. This reagent can be recovered and reused several times. Also it is readily prepared and could be stored for months without losing its potency. To study the effect of solvent, oxidation of benzenethiol was performed in different solvents. Acetonitrile is the best solvent due to the relatively good solubility of the catalyst and starting materials. To study the effect of solvent, oxidation of methyl phenyl sulfide was performed in different solvents. Actonitrile is the best solvent due to the relatively good solubility of the catalyst and starting materials. The effect of catalyst amount was investigated and the optimum ratio of reactant to oxidant (1:0.5) is found to be ideal for complete conversion of sulfides and thiols to the corresponded products [ABSTRACT FROM AUTHOR]

Thiol-Michael addition of thiophenol/thiobenzoic acid to 1,2,3-triazole linked chalcone was investigated under greener solvent-free condition. A simple one-pot multicomponent protocol has been achieved under mild conditions at ambient temperature in excellent yield. The protocol is advantageous as it is atom economic, cost-effective, eco-friendly, avoiding multi-step procedure and purification techniques. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) diabatic potential energy surfaces (PESs) of thiophenol involving the S0, and coupled 1ππ* and 1πσ* states were constructed by a neural network approach. Specifically, the diabatization of the PESs for the 1ππ* and 1πσ* states was achieved by the fitting approach with neural networks, which was merely based on adiabatic energies but with the correct symmetry constraint on the off-diagonal term in the diabatic potential energy matrix. The root mean square errors (RMSEs) of the neural network fitting for all three states were found to be quite small (<4 meV), which suggests the high accuracy of the neural network method. The computed low-lying energy levels of the S0 state and lifetime of the 0° state of S1 on the neural network PESs are found to be in good agreement with those from the earlier diabatic PESs, which validates the accuracy and reliability of the PESs fitted by the neural network approach. [ABSTRACT FROM AUTHOR]

Surface plasmon excitation at a nanogap between adjacent metal nanostructures generates extremely enhanced electric field, which enables us to detect and characterize individual molecules by surface enhanced Raman scattering (SERS). However, versatile nanogap fabrication methods have not been established, making difficult to efficiently exploit a gap mode plasmon in practical applications such as biosensing, biomedical, and environmental analyses. Here, we describe reproducible nanogap assemblies using adjacent metal nanoparticles (MNPs) and MNPs/adsorbates/metal substrates based on the Derjaguin − Landau − Verway − Overbeek theory and irreversible optical trapping of MNPs on metal substrates. The assembled nanogaps between adjacent MNPs, here, M is Ag or Au, enabled us to characterize adsorbates such as solvent shared ion pairs of hydrated metal ions, and three distinct adsorbed states of adenine depending on pH in aqueous solutions. Also we found plasmon-induced oxidation of p-alkyl thiophenol (p-AlkTP) at the nanogap on AgNP/p-AlkTP/Ag films. This oxidation has a specific reactivity at the p-position in the p-AlkTP phenyl ring, while providing intermediate species under nitrogen atmosphere. This specific oxidation is not driven by a thermal process but by a hot carrier transfer process. Thus, the nanogap fabrication methods using adjacent metal nanostructures we developed are promising to elucidate static and dynamical nature of target molecules using SERS spectroscopy. [ABSTRACT FROM AUTHOR]

Derivatives of sesquiterpene lactones modified at the lactone ring with a thiophenol residue have been synthesized. The resulting conjugates with thiophenol have capacity for the oxidation–elimination reaction by the action of ROS of a tumor cell with the release of initial cytotoxic lactones. It has been proposed to use the resulting sulfur-containing conjugates as ROS-activated prodrugs of sesquiterpene lactones. The antiproliferative properties of the conjugates have been examined on tumor and pseudonormal cell lines. The cytotoxicity of the conjugates is lower than that of parent lactones; however, in some cases, as with the conjugates of alantolactone with artemisiten, it remains moderate in all tumor cell lines tested. [ABSTRACT FROM AUTHOR]

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The development of photocatalytic intermolecular hydroamination reaction between N-aminated dihydropyridines and unactivated alkenes is reported. Metal-free co-catalysts, rhodamine 6G and thiophenol, in presence of visible light are used to initiate the process. The transformation shows a broad substrate scope, both alkenes and amidyl radical can act as coupling partners. The radical strategy provides excellent anti-Markovnikov selectivity and regioselectivity in diene substrates. [ABSTRACT FROM AUTHOR]

Thiophenol (PhSH) and its derivatives are useful chemicals for synthetic applications; however, they are highly toxic to humans and other organisms. In this work, we developed a novel near-infrared (NIR) fluorescent probe for sensing and imaging PhSH. The probe system displays several advantageous features, including NIR emission (centered at approximately 730 nm), a large Stokes shift (150 nm), a turn-on responding mode, high selectivity toward thiophenol, and a low detection limit (0.23 μM). Furthermore, practical tests revealed that the probe can be applied to monitor PhSH in tap, lake, and river water samples and living cells. [ABSTRACT FROM AUTHOR]

Some new transition metal chelates ([M(FSH)2] and [M(FSH) (CH3COO− or NO3−)], where M = Pd2+, VO2+, Mn2+, Zn2+, and cations) incorporating ferrocenyl thiophenol imine ligand (FSH) were prepared. Various spectral and physicochemical studies were performed to elucidate the geometric structure of the investigated compounds. The spectral data of FSH imine ligand and its metal chelates were explained concerning the structural changes due to complex formation. From the electronic spectra and the magnetic moments, the information about geometric structures can be concluded. The activation thermodynamic parameters of the thermal degradation for FSH complexes were calculated utilizing the method of Coats–Redfern. Correlation of all physicochemical tools employed in the investigation and DFT calculation, FSH imine ligand acts as a bidentate ligand and coordinates to Mn2+ in octahedral geometry, VO2+ in square pyramidal geometry, Pd2+ in square planner geometry and Zn2+ in distorted octahedral geometry. in vitro antimicrobial, anticancer and antioxidant activities of FSH ligand and its complexes were checked. All complexes exhibited superiority on the free ligand in successful treatment, specifically the FSHPd complex. The new complexes were subjected to study their DNA binding via various methods such as spectrophotometry, viscosity and gel electrophoresis. Their binding feature to ctDNA was proposed to be electrostatic, intercalation or replacement mode. Finally, the molecular docking studies were performed to understand the essence of the protein synthesized compounds' binding and binding affinity (PDB:3hb5). [ABSTRACT FROM AUTHOR]

Based on the thiolysis of dinitrophenyl ethers, a nucleus-targeted fluorescent probe, AQD, with bisalkylaminoanthraquinone as the fluorophore, was prepared for the near-infrared mapping of thiophenol in live cells, zebrafish, and mice. [ABSTRACT FROM AUTHOR]